There is a constant demand for economic and efficient ways to produce polymers. Controlled radical polymerization (hereinafter CRP), including single-electron transfer living radical polymerization (hereinafter SET-LRP) and atom transfer living polymerization (hereinafter ATRP), is a process which can produce various polymer products, in high yield, with functional, non-terminated ends, with high molecular weights, and with a low polydispersity index. Thus, there exists a need, however, for a CRP polymer process that is a convenient and economic route for producing functionalized branched block polymeric materials.